CN102356098A - Methods of preparing a polymerization catalyst - Google Patents
Methods of preparing a polymerization catalyst Download PDFInfo
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- CN102356098A CN102356098A CN2010800124786A CN201080012478A CN102356098A CN 102356098 A CN102356098 A CN 102356098A CN 2010800124786 A CN2010800124786 A CN 2010800124786A CN 201080012478 A CN201080012478 A CN 201080012478A CN 102356098 A CN102356098 A CN 102356098A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/22—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/69—Chromium, molybdenum, tungsten or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Abstract
A method comprising (a) contacting a support and a chromium-containing compound to form chromium-containing support, (b) heat treating the chromium-containing support in an oxidizing atmosphere to form a treated support, (c) contacting the treated support with carbon monoxide to form a CO-contacted support, and (d) contacting the CO-contacted support with hydrogen to form a catalyst. A method comprising oxidizing a chromium-treated support to form a polymerization catalyst, contacting the polymerization catalyst with carbon monoxide to form a reduced polymerization catalyst, contacting the reduced polymerization catalyst with hydrogen to form an activated polymerization catalyst, and contacting the activated polymerization catalyst with ethylene in a reaction zone under suitable reaction conditions to form a random copolymer. A method comprising reducing a polymerization catalyst comprising Cr(VI) to form a polymerization catalyst comprising Cr(II), and treating the polymerization catalyst comprising Cr(II) with hydrogen.
Description
Technical field
The disclosure relates generally to polymerizing catalyst.More specifically, the disclosure relates to a kind of preparation method of polymerizing catalyst of load chromium.
Background technology
Polymerizing catalyst is well-known, yet the method for making these catalyzer all has various defectives.Polymerizing catalyst preparing method's raising can reduce the cost relevant with Catalyst Production and improve process economy property.Thereby, need to continue the novel method of development and preparation polymerizing catalyst.
General introduction
Herein disclosed is a kind of method; Comprise that (a) makes carrier and contain chromium cpd and contact with formation and contain the chromium carrier; (b) thermal treatment contains the chromium carrier to form the processing carrier in oxidizing atmosphere; (c) with carbon monoxide contact handle carrier with form the CO-contact carrier and (d) with contacted with hydrogen CO-contact carrier to form catalyzer.
This paper also discloses a kind of method; Comprise that chromic oxide-processing carrier is to form polymerizing catalyst; Contact polymerizing catalyst to form the reductive polymerization catalyzer with carbon monoxide; With contacted with hydrogen reductive polymerization catalyzer to form the activated polymerization catalyzer; And the contact activation polymerizing catalyst is to generate random copolymers under the situation that no promotor exists with ethene in the reaction zone under being fit to reaction conditions, and wherein the comonomer original position produces.
This paper further discloses a kind of method, comprises that polymerizing catalyst that reduction contains Cr (VI) contains the polymerizing catalyst of Cr (II) with formation, and contains the polymerizing catalyst of Cr (II) with hydrogen treat.
Detail
Though should be appreciated that the illustrative execution that one or more embodiments hereinafter are provided at the beginning, no matter can use is present known or already present any some technology implementations system of the present disclosure and/or method.The technology that the disclosure should never be limited to said illustrative enforcement, figure and hereinafter set forth comprises exemplary design and enforcement that this paper sets forth and describes, but can in the four corner that falls into the accompanying claims scope and the equivalent form of value thereof, make amendment.
Herein disclosed is a kind of preparation method of supported chromium catalysts, this supported chromium catalysts is with carbon monoxide (CO), hydrogen (H) order contacts then, and this paper is called the CO/H catalyzer.In one embodiment, a kind of method of the CO/H of preparation catalyzer comprises that containing the chromium cpd contact carrier with one or more contains the chromium carrier with formation.Can thermal treatment contain the chromium carrier to make the processing carrier.Can handle carrier to make the CO-contact carrier with carbon monoxide (CO) contact then.Then can be with contacted with hydrogen CO-contact carrier to make the CO/H catalyzer, it can be used as polymerizing catalyst.
In one embodiment, the CO/H catalyzer can comprise arbitrary suitable carrier.The instance that is fit to carrier includes but not limited to silicon-dioxide, titanium dioxide, aluminum oxide, aluminum phosphate or its composition.Carrier can have effective surface-area and pore volume so that active CO/H catalyzer to be provided.
Can use any suitable method to prepare carrier.For example, the preparation alumina supporter can be with or without positively charged ion and aluminium through deposition sodium aluminate to form the aluminum oxide (also being called as boehmite) that chemical formula is (AlOOH).The preparation silica supports for example can be through using the sour aqueous solution that contacts alkalimetal silicate to form silica hydrogel.Carrier also can comprise other component that the CO/H catalyzer is had no adverse effect, like Thorotrast, Natural manganese dioxide, fluorochemical, silicate, vitriol, phosphoric acid salt, zirconium white, titanium dioxide, ceria, clay, zeolite or its composition.
Carrier also can contain other metal oxide, like titanium dioxide, zirconium white, boron oxide (boria), phosphoric acid salt etc.These other metal oxides can add through any currently known methods in this area by means of present disclosure, as being undertaken cogelled by anhydrous or aqueous solvent or dipping.In one embodiment, said other metal oxide can exist with following content in carrier: the extremely about 20wt.% of about 0wt.% of carrier, or about 1wt.% by weight is to about 10wt.%, or the extremely about 80wt.% of about 2wt.%.
In one embodiment; Carrier can exist with following content in the CO/H catalyzer: (wt.%) by weight; About 50% to about 99% carrier of CO/H catalyzer, alternatively approximately 75wt.% to about 99wt.%, alternatively approximately 90wt.% to about 99wt.%.Here, vehicle weight per-cent refers to behind all processing steps the final weight per-cent with the total restatement of the CO/H catalyzer carrier relevant with the CO/H catalyzer.
In one embodiment, the CO/H catalyzer contains chromium.Can be through chromium being introduced in the CO/H catalyzer with one or more components (like carrier) that contain chromium cpd contact CO/H catalyzer.Contain chromium cpd and can be one or more compounds that contain sexavalence oxidation state chromium (following be Cr (VI)) or contain the material that is fit to be converted into Cr (VI).In one embodiment, contain chromium cpd and comprise water soluble ge cpd; Alternatively, contain chromium cpd and comprise hydrocarbon dissolubility chromium cpd.Containing chromium cpd can be chromium (II) compound, chromium (III) compound or its composition.Chromium (III) compound that is fit to includes but not limited to carboxylic acid chromium, chromium naphthenate, hafnium halide, minaline chromium (chromium pyrroide), phenylformic acid chromium, two ketone acid chromium (chromium dionate), chromium nitrate, chromium sulphate or its composition.Concrete chromium (III) compound includes but not limited to isocaprylic acid chromium (III), 2; 2; 6; 6 ,-tetramethyl-heptane diketone chromium (III), chromium naphthenate (III), chromium chloride (III), three (2 ethyl hexanoic acid) chromium (III), chromium fluoride, oxo-2 ethyl hexanoic acid chromium (III), Dichloroethyl caproic acid chromium (III), chromium acetylacetonate (III), chromium acetate (III), chromium butyrate (III), PIVALIC ACID CRUDE (25) chromium (III), lauric acid chromium (III), chromium sulphate (III), chromium+oxalic acid (III), phenylformic acid chromium (III), minaline chromium (III), perchloric acid chromium (III), chloric acid chromium (III) or its composition.Chromium (II) compound that is fit to includes but not limited to Chromous Fluoride, chromous chloride, chromous bromide, chromous iodide, two (2 ethyl hexanoic acid) chromium (II), chromium acetate (II), chromium butyrate (II), PIVALIC ACID CRUDE (25) chromium (II), lauric acid chromium (II), chromium stearate (II), chromium+oxalic acid (II), phenylformic acid chromium chromium (II), minaline chromium (II), chromous sulfate or its composition.Other instance that contains chromium cpd that is fit to comprises the chromic acid tertiary butyl ester in the hydrocarbon liquid; Chromium trioxide in the water; Chromium acetate in the water; Chromium nitrate in the alcohol; Zeroth order organo-chromium compound such as π key chromium complex, for example two cumene chromium and dibenzene-chromiums; Or its composition.π key chromium complex is at U.S. Patent number 3,976, description arranged in 632, and this paper all incorporates into it by reference.
The content range of the chromium that exists in the CO/H catalyzer can for about 0.01wt.% of CO/H catalyzer by weight to the about chromium of 10wt.%; About alternatively 0.2wt.% is to the chromium of about 5wt.%; About alternatively 0.5wt.% is to the chromium of about 2wt.%, about alternatively 1% chromium.The weight percent of chromium refers to behind all processing steps the final weight per-cent by total restatement of catalyzer chromium relevant with catalyzer here.
In one embodiment, a kind of method of the CO/H of preparation catalyzer comprises that containing the chromium cpd contact carrier with one or more contains the chromium carrier with formation.Carrier can be this paper aforementioned type with containing chromium cpd.Can use any suitable method to contact, for example through ion-exchange, initial stage humidifying, filling perforation, water-based dipping, organic solvent dipping, melt coating, cogelled etc.In some embodiments, but be used to prepare precalcining carrier before the CO/H catalyzer (for example, containing before chromium cpd contains the chromium carrier with formation) in contact.For example; Through heating under the situation about existing at air; The precalcining carrier; Temperature is scope between about 300 ℃ to about 1000 ℃; Or scope between about 400 ℃ to about 800 ℃, or scope between about 500 ℃ to about 700 ℃, the time is about 1 minute to about 10 hours; Or about 20 minutes to about 5 hours, or about 1 hour to about 3 hours.Thereafter, the carrier of precalcining can with contain chromium cpd and contact with formation and contain the chromium carrier.
Can thermal treatment contain the chromium carrier to form the processing carrier.In one embodiment; Implement thermal treatment under the temperature in following ranges: between about 400 ℃ to about 1000 ℃; Or between about 500 ℃ to about 800 ℃; Or between about 500 ℃ to about 750 ℃; Time is about 1 minute to about 24 hours; Or about 1 to about 10 hours, or about 2 to about 8 hours, handle carrier to form.Can use any suitable method to implement the thermal treatment of carrier, the for example rheomorphism in the presence of oxidizing atmosphere such as oxygen or air.Do not hope that by one theory the thermal treatment that contains the chromium carrier can cause that the content of 6-valence Cr ions that is present in the catalyzer increases.
Then, can handle carrier to make the CO-contact carrier with carbon monoxide (CO) contact.In one embodiment; Can use any suitable method to implement and the contacting of CO; Like fluidisation; Its temperature is about 250 ℃ to about 750 ℃; Or about 300 ℃ to about 600 ℃; Or about 350 ℃ to about 500 ℃, and the time be about 1 minute to about 10 hours or about 10 minutes to about 5 hours or about 30 minutes to about 2 hours.Do not hope by one theory, under disclosed condition, handle carrier and can cause that Cr (VI) is reduced to Cr (II) with the CO contact.
Then, can be with contacted with hydrogen CO-contact carrier to make the CO/H catalyzer.In one embodiment; Enforcement is about 25 ℃ to about 750 ℃ with the temperature of contacted with hydrogen; Or about 100 ℃ to about 500 ℃ or about 150 ℃ to about 350 ℃; Time is about 1 minute to about 10 hours or about 10 minutes to about 5 hours or about 30 minutes to about 2 hours, and pressure is that extremely about 50 crust of about 0.1 crust (bar) or about 0.5 crust to about 25 crust or about 1 cling to about 3 crust.The material that is obtained is the CO/H catalyzer, and it can play the effect of polymerizing catalyst when being used for polymerization reaction system.
In one embodiment, the aforesaid one or more steps of this paper that are used for preparing the CO/H catalyzer can be carried out at reactor or reactor system.In an optional embodiment, the aforesaid one or more steps of this paper that are used to prepare the CO/H catalyzer can be carried out outside reactor or reaction system.In this embodiment, can adjust the formation that one or more preparation parameters (as with contacted with hydrogen CO-contact carrier) are beneficial to the CO/H catalyzer.For example can be with the said CO-contact carrier of hydrogen treat to make the CO/H catalyzer.The processing of CO-contact carrier can be carried out before catalyzer is introduced into reactor, as in activator or in any suitable container (like preparatory contacting container), or in reactor, carried out.In this embodiment, can be with the temperature range of hydrogen treat CO-contact carrier at about 25 ℃ to about 500 ℃ or about 75 ℃ to about 350 ℃ or about 100 ℃ to 250 ℃.Implementing the hydrogen pressure scope of CO-contact carrier processing can cling to about 3 crust at extremely about 50 crust of about 0.1 crust or extremely about 25 crust of about 0.5 crust or about 1.(being temperature, hydrogen pressure) implemented can be about 1 minute to about 24 hours or about 10 minutes to about 5 hours or about 15 minutes to about 2 hours with the time of hydrogen treat CO-contact carrier in addition, under the described conditions.After hydrogen treat, can hydrogen removed from material and make material blow off hydrogen through any suitable method, as through being exposed to the competent time of inert gas to remove hydrogen.
In one embodiment, the CO/H catalyzer is the component that contains the catalysis system of promotor.Normally, promotor can be any organometallic compound that can activate and/or strengthen the performance of catalyzer described herein (being the CO/H catalyzer) with olefin polymerization.The promotor that is fit to can comprise monomeric or oligomeric metal alkylide, metal arylide, the alkyl-metal arylide of the metal that contains at least a B of being selected from, Al, Be, Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs, Zn, Cd and Sn.In one embodiment, promotor comprises metal alkylide such as boron alkyl, aluminum alkyls, zinc alkyl(s), lithium alkylide, sodium alkyl, alkyl magnesium and composition thereof.Alternatively, promotor comprises boron alkyl.Metal alkylide can have any carbonatoms.But because commercial availability and ease for use, common each the metal alkylide molecule of metal alkylide contains and is less than about 70 carbon atoms, and per molecule is less than 20 carbon atoms alternatively.In one embodiment, promotor comprises having about 1 boron alkyl to the hydrocarbyl group of about 12 carbon.Promotor can directly be introduced into reaction zone or can before forming the catalyst mixture be introduced into reaction zone subsequently, contact with the CO/H catalyzer with the CO/H catalyzer together.In one embodiment, promotor can exist with following content: about 0.1ppm is 50ppm extremely approximately, and about alternatively 1ppm is to about 20ppm, and about alternatively 2ppm is to about 10ppm.
In optional embodiment, the CO/H catalyzer is the component that lacks the catalysis system of promotor.When all existing other similar reaction of implementing down to compare with catalyzer and promotor, this embodiment of CO/H catalyzer catalyzed reaction (for example polyreaction) under no promotor can cause the improvement of overall process economy.Though promotor is useful sometimes, also possibly bring undesired result, like the reduction of the expansion of molecular weight distribution (MWD), higher long chain branching (LCB) or melt index (MI).In one embodiment, the CO/H catalyzer allows not use promotor and the in-situ preparing comonomer.
The disclosed catalyzer of this paper (being the CO/H catalyzer) and catalyst system are intended and are used for any olefine polymerizing process that can use all kinds polymerization reactor to carry out.Use like this paper, " polymerization reactor " comprise can polymerization of olefin monomers making any polymerization reactor of homopolymer and multipolymer.This homopolymer and multipolymer refer to resin or polymkeric substance.
Various types of reactors comprises those that can be called batch reactor, slurry-phase reactor, Gas-phase reactor, solution reactor, high-pressure reactor, tubular reactor or high pressure tank reactor.Gas-phase reactor can comprise fluidized-bed reactor or multistage horizontal reactor.Slurry-phase reactor can comprise the loop of vertical or level.High-pressure reactor can comprise autoclave or tubular reactor.Type of reactor can comprise batch process or continuous processing.Continuous processing can be used intermittently or successive product blowing.Method also can comprise the part or all of direct recirculation of unreacted monomer, unreacted comonomer and/or thinner.
Polymerization reactor system of the present disclosure can comprise a kind of type of reactor or a plurality of reactors of of the same race or different sorts type in the system.Polymkeric substance manufacturing in a plurality of reactors can comprise several stages, wherein at least two independently polymerization reactor is interconnection through transmitting device, this makes the polymkeric substance that is produced by first polymerization reactor transfer to second reactor becomes possibility.Polymerizing condition a reactor desired can be different with the operational condition of another reactor.Alternatively, for successive polymerization, the polymerization in a plurality of reactors can comprise from the reactor of the artificial transfer polymerization thing of a reactor to back.A plurality of reactor assemblies can comprise any combination, include but not limited to combination, a plurality of high-pressure reactor of a plurality of loop reactors, a plurality of gas reactor, loop and gas reactor or have the combination of the high pressure and/or the gas reactor in loop.Can move a plurality of reactors by serial or parallel connection.
According to an aspect of the present disclosure, polymerization reactor system can comprise at least one loop slurry reactor that contains horizontal or vertical loop.Monomer, thinner, catalyzer and randomly any comonomer feed into serially and carry out in the polymeric loop reactor.Normally, successive processes can comprise that monomer, catalyzer and thinner are introduced polymerization reactor continuously and removed the suspension that contains polymer beads and thinner by this reactor continuously.The reactor discharge can be flashed, in the liquid that contains thinner, monomer and/or comonomer, to remove solid polymer.Various technology can be used for this separating step, include but not limited to comprise any bonded flash distillation of heating and step-down; Whirlwind effect through in cyclonic separator or wet cyclone separates; Or through centrifugation.
Typical slurry phase polymerisation process (being also referred to as particle formation method) is open for example at United States Patent (USP) 3,248, and 179,4,501,885,5,565; 175,5,575,979,6,239,235,6; In 262,191 and 6,833,415, this paper by reference with it each a piece of writing all incorporate into it.
It is the hydrocarbon of liquid that the suitable thinner that in slurry polymerization, uses includes but not limited to by monomer polymerized with under reaction conditions.The instance that is fit to thinner includes but not limited to hydrocarbon, for example propane, hexahydroaniline, Trimethylmethane, normal butane, Skellysolve A, iso-pentane, neopentane, normal hexane.Some loop polymerization reactions can be carried out under the bulk conditions of not using thinner.The polymerization that instance is a propylene monomer is anti-, and is disclosed in 314 as at United States Patent (USP) 5,455, all incorporates this paper into it by reference.
According to another aspect of the present disclosure, polymerization reactor can comprise at least one Gas-phase reactor.This system can when catalyzer exists, use and contain one or more monomeric continuous recirculation flows that cycle through fluidized-bed continuously under polymerizing condition.Recirculation flow can be withdrawn from also recirculation from fluidized-bed and get back in the reactor.Side by side, can reclaim polymer product and add new or fresh monomer from reactor to replace monomer polymerized.This Gas-phase reactor can comprise the process of the multistep vapour phase polymerization of alkene, wherein at least two independently vapour phase polymerization district internal olefin carry out polymerization with gas phase, the polymerization catalyst thing that contains that will in first polymeric area, generate simultaneously feeds into second polymeric area.At United States Patent (USP) 5,352, one type Gas-phase reactor is disclosed in 749,4,588,790 and 5,436,304, this paper by reference with it each piece of writing all incorporate into it.
According to another aspect of the invention, pressure polymerization reactor can comprise tubular reactor or autoclave reactor.Tubular reactor can have the several districts that add new monomer, initiator or catalyzer.Monomer can be entrained in the inert gas and be introduced into a district of reactor.Initiator, catalyzer and/or catalyst component can be entrained in the air-flow and be introduced into another district of reactor.Can mix these air-flows so that polymerization.Suitably use heat and pressure are to obtain the polymeric reaction condition of optimization.
According to another aspect of the present disclosure, polymerization reactor can comprise solution polymerization reactor, and wherein monomer contacts with catalyst composition through stirring or other modes that is fit to.Can adopt the carrier that contains inertia organic thinner or excess monomer.If need, under liquid substance existence or non-existent situation, monomer is contacted with catalytic reaction products with gas phase.Polymeric area is maintained under the temperature and pressure that causes the solution of formation polymkeric substance in reaction medium.Can adopt stirring in whole polymeric area, to obtain the polyblend that homogeneous was controlled and kept to better temperature.Adopt the method that is fit to disperse the polymeric heat release.
Be applicable to that polymerization reactor of the present disclosure can further comprise the feed system of at least one raw material feed system, at least one catalyzer or catalyst component and/or arbitrary combination of at least one polymer recovery system.The reactive system that the disclosure is suitable for can further comprise be used for feed purification, catalyzer storage and prepare, extrude, the system of reactor cooling, polymer recovery, classification, recirculation, storage, output, lab analysis and process control.
The condition of controlling with resin properties is provided for polymerization efficiency comprises temperature, pressure and various concentration of reactants.Polymerization temperature can influence catalyst production, polymericular weight and molecular weight distribution.According to the Gibbs free energy equation, suitable polymerization temperature can be the following arbitrary temperature of depolymerization temperature.Usually, according to the type of polymerization reactor, this can comprise as about 60 ℃ to about 280 ℃ and about 70 ℃ to about 110 ℃.
The pressure that is fit to also changes according to reactor and polyreaction type.Usually, the pressure of liquid polymerization is less than 1000psig in loop reactor.Vapour phase polymerization pressure usually about 200 to about 500psig.High pressure polymerisation in tubulose or the autoclave reactor moves between about 75000psig about 20000 usually.The supercritical range operation that polymerization reactor also can take place under common higher temperature and pressure.The operation of (supercritical phase) can bring benefit more than Pressure/Temperature figure stagnation point.
Each reactant concn of may command has the resin of certain physical and mechanical property with manufacturing.The end-use product that passes through resins that is proposed has determined required resin property with the method that forms this product.Mechanical property comprises stretching, deflection, bump, creep, stress relaxation and hardness test.Physicals comprises density, molecular weight, molecular weight distribution, temperature of fusion, second-order transition temperature, crystalline melting temperature, density, stereospecicity, crack growth, long chain branching and flow measurement.
The concentration of monomer, comonomer, hydrogen, properties-correcting agent and electron donor(ED) is important in the performance of these resins of preparation.Comonomer is used to control product density.Hydrogen is used to control molecular weight product.Properties-correcting agent is used to control product performance and electron donor(ED) influences stereospecicity.In addition, because poisonous substance influence reaction and product performance, concentration of poisons should minimize.In one embodiment, between polymerization period, add hydrogen to reactor.Alternatively, between polymerization period, do not add hydrogen to reactor.
Polymkeric substance or resin can be made into various article, include but not limited to bottle, drum, toy, household receptacle, utensil, membrane product, drum, fuel tank, pipe, mulch film and liner.Can in all sorts of ways and process these article, include but not limited to blow moulding, extrusion molding, rotational molding, injection molding, fiber sprinning, thermoforming, casting etc.After the polymerization,, can add additive and properties-correcting agent in polymkeric substance for better processing being provided during manufacture and in end product, obtaining desired properties.Additive comprises the surface-modifying agent like slip(ping)agent, anti-hard caking agent, tackifier; Antioxidant like primary antioxidant and secondary antioxidant; Pigment; Processing material like wax/oil and fluoroelastomer; With special additive like fire retardant, static inhibitor, scavenging agent, absorption agent, smell toughener and degradation agents.
The polymerization that can be used for alkene according to the catalyzer and the catalyst system of disclosure preparation is like alpha-olefin.In one embodiment, under being fit to reaction conditions, contact CO/H catalyzer or catalyst system so that olefinic polymerization with one or more alkene in the reaction zone of (like temperature, pressure etc.).Straight or branched alpha-olefin with 2 to 30 carbon atoms can be used as olefin feedstock.The specific examples of alpha-olefin can comprise ethene, propylene, 1-butylene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene etc.Can use this alpha-olefin (as making homopolymer) separately or with two kinds or more kinds of various enforcement usefulness that are combined into, to make multipolymer (like dimer, tripolymer etc.).In one embodiment, the CO/H catalyzer is used to make Vilaterm, like Natene or multipolymer.In various embodiments, ethene uses with one or more comonomers like 1-octene, 1-hexene, 1-butylene etc.
In one embodiment; The density of only using the homopolymer that does not add the 1-hexene in ethylene raw and the reactor, makes through the CO/H catalyzer can be approximately 0.935g/cc to about 0.959g/cc; About alternatively 0.95g/cc is to about 0.958g/cc, or about alternatively 0.958g/cc is to about 0.95g/cc.The further characteristic of this polymkeric substance can be high load melt index (HLMI); Its scope was at approximately 1g/10 minute to approximately 250g/10 minute; Alternatively at approximately 5g/10 minute to approximately 250g/10 minute, alternatively at approximately 10g/10 minute to approximately 250g/10 minute.According to U.S. test and materials association (ASTM) D1238 identification, HLMI refers to when when receiving the power of 21600g for 190 ℃, and molten plastic resin is the flow velocity in 0.0825 inch hole through diameter.
In another embodiment, when contacting with the alpha-olefin raw material of mainly being made up of ethene, the CO/H catalyzer can original position produce comonomer under the situation of no promotor, generate copolymer products.In this embodiment, the polymer phase that the in-situ copolymerization monomer system of the characteristic of copolymer products and use promotor produces seemingly.For example, the polymer phase of the in-situ copolymerization monomer system preparation of molecular weight distribution, long chain branching and the melt index potential of the polymkeric substance that obtains (melt index potential) and use promotor seemingly.
In one embodiment, CO/H catalyst type as herein described is used under the situation of no external interpolation comonomer, making copolymer products.Do not hope by one theory, contact with monomer before with H
2Pre-treatment Cr (II) makes the disclosed CO/H catalyzer of this paper, then not only can be oligomeric but also polymerizable olefin to generate copolymer products.
In another embodiment, the CO/H catalyzer also can add the random copolymers (RCP) that is used to make ethene and comonomer in other comonomer such as 1-hexene to the reactor through the outside.The density of RCP can be the extremely about 0.96g/cc of about 0.92g/cc, is extremely approximately 0.96g/cc of about 0.93g/cc alternatively, is the extremely about 0.955g/cc of about 0.94g/cc alternatively.
In this embodiment; The content of the comonomer that exists among the RCP (like the 1-hexene) can be based on the extremely about 15wt.% of about 0.1 weight percent (wt.%) of RCP gross weight; Approximately 0.5wt.% is to about 10wt.% alternatively, and about alternatively 1wt.% is 5wt.% extremely approximately.
In one embodiment, the CO/H catalyzer can be used for manufacturing and contains the trimerical product of alkene.In some embodiments, the CO/H catalyzer is used for making the reactor effluent that contains ethylene trimerization body (hexene).In other embodiments, the manufacturing of CO/H catalyzer contains the reactor effluent of 1-hexene.In other embodiments, the CO/H catalyzer is used to make the reactor effluent that is rich in the 1-hexene.In other embodiments, the CO/H catalyzer is used to make wherein that the 1-hexene is the reactor effluent of main ingredient.
In one embodiment, when as polymerizing catalyst, CO/H catalyst type as herein described has shown and the suitable product yield of catalyst system that contains other similar catalyzer and promotor.In one embodiment; The product yield that the CO/H catalyzer has is that about 500g polymkeric substance/g catalyzer (g/g) is to about 10000g/g; About alternatively 1000g/g is to about 5000g/g; About alternatively 2000g/g is to about 4000g/g; And the polymerization activity that has for every gram catalyzer 1000g polymkeric substance (g/g-h) approximately per hour to about 5000g/g-h; Being extremely approximately 5000g/g-h of about 1500g/g-h alternatively, is that about 2000g/g-h is to about 5000g/g-h alternatively.
When as polymerizing catalyst, CO/H catalyst type described herein itself can be made comonomer.In one embodiment, under the situation of no promotor, use CO/H catalyst type described herein to prepare RCP by ethene.In addition, the RCP comonomer can contain the 1-hexene, and comonomer mainly is made up of the 1-hexene alternatively.In this embodiment, the RCP that obtains when containing the polymkeric substance comparison of catalyst system manufacturing of other similar catalyzer and promotor, can contain narrower molecular weight distribution (MWD) with use.The RCP that obtains show the long chain branching (LCB) of reduction with using comparing of other similar polymerizing catalyst and promotor manufacturing.Suitable with the catalyst system that contains other similar catalyzer and promotor, use the RCP of CO/H catalyst type described herein manufacturing to improve and/or to eliminate typically to be present in RCP make in the defective relevant with wax and/or cigarette.
Embodiment
Describe, in general terms embodiment, provide the following example as embodiment of the present disclosure and be used to illustrate its practical and advantage.Should be appreciated that embodiment be through the explanation mode provide and be not intended to limit by any way specification sheets or claim.
Embodiment 1
Studied the performance of Cr-supported catalyst in vinyl polymerization.Use 7 samples of 969MPI preparation, be appointed as sample 1-7,969MPI is the silicon dioxide carried Cr catalyzer that can get from W.R.Grace commerce, has 300m
2The surface-area of/g, the pore volume of 1.6mL/g and about 100 microns mean particle size.Sample 1-6 through rheomorphism thermal treatment 3 hours, reduces half an hour through rheomorphism in 350 ℃ of dry CO in 800 ℃ of dry airs then.Then in 100 ℃ lab scale reactor (bench reactor) with the ethene of 550psi specimen 1,3 and 5 polymerization separately in 1 hour.With hydrogen treat sample 2 and 4 (promptly after handling with carbon monoxide in advance again with hydrogen treat), the ethene with 550psi is tested its polymerization separately in 100 ℃ lab scale reactor then.Equally with hydrogen treat sample 6 (promptly carbon monoxide handle back), test in 105 ℃ lab scale reactor ethene with 550psi its polymerization of test separately in 1 hour then.800 ℃ of heat treated sample 7, and at 350 ℃ with H
2Reduction half an hour (promptly not handling with CO in advance), then under above-mentioned simulated condition at similar its polymerization of lab scale reactor build-in test.The polyreaction continuous service filled up polymkeric substance in reactor, as about 24 to about 70 minutes.About sample 6, the same hydrogen that adds in the reactor.Record is listed in the table 1 by polyethylene production, reaction times, polymerization activity, HLMI and the density of each sample acquisition and with the result.
Table 1
*Processing refer to be used to make final catalyzer institute in steps, comprise that thermal treatment, CO handle, H
2Handle
The result shows that density and the sample 1 of the sample 2-6 of preheating in hydrogen relatively reduce.Show like sample 3 and 4, at 250 ℃ reaction conditionss as if near the optimal temperature of hydrogen treat.Show that like sample 5 the interior interpolation of reactor hydrogen shows very little or do not have adjection.In addition, show, omit the bad catalyzer that the CO reduction step causes low PE output, low activity, high-density and low HLMI simply with the hydrogen reducing catalyzer like sample 7.
Secondly, analyze by the polymkeric substance of sample 2 and 6 gained content with C-13NMR with hexene co-monomer in the mensuration polymkeric substance.The weight percent of record 1-octene, 1-hexene, 1-butylene and relevant monomer dispersity (RMD) are also listed in the result in the table 2.
Table 2
The result shows, and is that the 1-hexene is that original position produces in reactor and get into the primary product in the polymkeric substance.In addition, two polymkeric substance all have the RMD greater than 100%, and it demonstrates the uniform distribution of branching.
Although shown and described embodiment of the present disclosure, can improve not breaking away under disclosure spirit and the instruction.Embodiment described herein only is exemplary, and it is restrictive being not intended.Many variations of the present disclosure disclosed herein and improvement all are possible and fall in the disclosure scope.Clearly stating the digital scope or the place of restriction, be to be understood that this clear and definite scope or restriction comprise fall into repetition scope or the restriction of scope or the same level in the restriction of clear expression (comprise 2,3,4 etc. as about 1 to about 10; Comprise 0.11,0.12,0.13 etc. greater than 0.10).For example, has lower bound R as long as disclose
LWith high limit R
UDigital scope, any numeral that falls in this scope is promptly disclosed particularly.Especially, the following column of figure in the scope is by open particularly: R=R
L+ k* (R
U-R
L), wherein k is the parameter that has 1% increment between 1% to 100% scope, as k be 1%, 2%, 3%, 4%, 5% ..., 50%, 51%, 52% ..., 95%, 96%, 97%, 98%, 99% or 100%.Moreover, the digital any digital scopes that limited 2 R of above definition are also specifically disclosed.Relevant with any key element of claim, using term " alternatively " to mean needs or does not need alternatively this key element.These two alternativess are intended and being fallen in the claim scope.As the use that broad terms such as comprises, comprises, has should be understood to as by ... Form, basically by ... Form, essence by ... Narrow sense terms such as composition provide support.
Therefore, protection domain is not limited by foregoing description and is only limited by claim, and this scope comprises all equivalent form of values of claim theme.Each is merged in the specification sheets as an embodiment of the present disclosure with each claim.Like this, what is claimed is further description and be additional to disclosure embodiment.Discussion for citing document is not to admit that it is a prior art of the present disclosure, particularly possibly have any citing document of open day behind the application's priority date.The disclosure of all patents, patent application and public publication that this paper quotes is incorporated this paper into by reference at this, and to be them to this paper illustrated provide the degree of quoting that exemplary, procedural or other details is replenished.
Claims (22)
1. method comprises:
(a) make carrier and contain chromium cpd and contact with formation and contain the chromium carrier;
(b) the said chromium carrier that contains of thermal treatment is handled carrier to form in oxidizing atmosphere;
(c) contact said processing carrier to form the CO-contact carrier with carbon monoxide; With
(d) with the said CO-contact carrier of contacted with hydrogen to form catalyzer.
2. the described method of claim 1, wherein said carrier comprises silicon-dioxide, titanium dioxide, zirconium white, boron oxide, phosphoric acid salt, aluminum oxide, aluminum phosphate or its composition.
3. the described method of claim 1, wherein said carrier can be to exist to the about amount of 99wt.% by the about 50wt.% of the final weight of said catalyzer in said catalyzer.
4. the described method of claim 1, the wherein said chromium cpd that contains comprises water soluble ge cpd, hydrocarbon dissolubility chromium cpd, chromium (II) compound, chromium (III) compound or its composition.
5. the described method of claim 1, wherein chromium in said catalyzer to exist to the about amount of 10wt.% by the about 0.01wt.% of the final weight of said catalyzer.
6. the described method of claim 1, wherein said thermal treatment be included in about 400 ℃ to about 1000 ℃ temperature about 1 minute of heating to about 24 hours time.
7. the described method of claim 1, wherein said thermal treatment is carried out in the presence of oxygen, air or its its composition.
8. the described method of claim 1 is wherein saidly carried out about 1 minute to about 10 hours time at about 250 ℃ with the carbon monoxide contact to about 750 ℃ temperature.
9. the described method of claim 1 is wherein saidly carried out about 1 minute to about 10 hours time at about 25 ℃ with contacted with hydrogen to about 750 ℃ temperature, and carries out to the pressure of about 50 crust at about 0.1 crust.
10. the described method of claim 1, wherein said catalyzer have about 1000g/g-h to the about polymerization activity of 5000g/g-h.
11. the described method of claim 1 further is included in the reaction zone that is fit under the reaction conditions and contacts said catalyzer to generate polymkeric substance and in said reaction zone, to reclaim said polymkeric substance with one or more olefinic monomers.
12. the described method of claim 11, wherein said olefinic monomer comprise that ethene and said polymkeric substance comprise Alathon; Said olefinic monomer comprises that ethene and another 'alpha '-olefin monomers and said polymkeric substance comprise ethylene copolymer; Or its combination.
13. the described method of claim 11, wherein said polymkeric substance have about 1g/10 minute to about 250g/10 minute high load melt index (HLMI).
14. the described method of claim 11, wherein said polymkeric substance have the yield of about 500g/g to about 10000g/g.
15. the described method of claim 11, wherein said polymkeric substance have the density of about 0.920g/cc to about 0.96g/cc.
16. the described method of claim 1, wherein step (a) and (b), (c), (d) or its are combined in reactor and carry out outward.
17. a method comprises:
Chromic oxide-processing carrier is to form polymerizing catalyst;
Contact said polymerizing catalyst to form the reductive polymerization catalyzer with carbon monoxide;
With the said reductive polymerization catalyzer of contacted with hydrogen to form the activated polymerization catalyzer; With
In being fit to reaction conditions reaction zone down with the situation of ethene at no promotor under the said activated polymerization catalyzer of contact with the generation random copolymers, wherein comonomer original position generation.
18. the described method of claim 17, wherein random copolymers is the Vilaterm with hexene side chain.
19. the described method of claim 18, wherein said hexene side chain exist with the amount based on the extremely about 15wt.% of the about 0.1wt.% of the gross weight of said Random copolymer RCP in said Random copolymer RCP.
20. a method comprises:
The polymerizing catalyst that reduction contains Cr (VI) contains the polymerizing catalyst of Cr (II) with formation; With
With the said polymerizing catalyst that contains Cr (II) of hydrogen treat.
21. catalyzer through the described method preparation of claim 1.
22. the described method of claim 1 further is included in and contacts said catalyzer with the raw material of mainly being made up of ethene under the condition that is fit to vinyl polymerization and recovery has the polymeric composition of about 0.935g/cc to about 0.958g/cc density.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/406,109 | 2009-03-17 | ||
| US12/406,109 US7910669B2 (en) | 2009-03-17 | 2009-03-17 | Methods of preparing a polymerization catalyst |
| PCT/US2010/000778 WO2010107478A1 (en) | 2009-03-17 | 2010-03-15 | Methods of preparing a polymerization catalyst |
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| Publication Number | Publication Date |
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| CN102356098A true CN102356098A (en) | 2012-02-15 |
| CN102356098B CN102356098B (en) | 2014-11-05 |
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| US (2) | US7910669B2 (en) |
| EP (1) | EP2408826B1 (en) |
| KR (1) | KR101667830B1 (en) |
| CN (1) | CN102356098B (en) |
| BR (1) | BRPI1009883A2 (en) |
| CO (1) | CO6571848A2 (en) |
| ES (1) | ES2543609T3 (en) |
| MX (1) | MX2011009795A (en) |
| SG (1) | SG174405A1 (en) |
| WO (1) | WO2010107478A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114401788A (en) * | 2019-09-16 | 2022-04-26 | 切弗朗菲利浦化学公司 | Chromium-based catalysts and processes for converting alkanes to higher and lower aliphatic hydrocarbons |
| WO2023051580A1 (en) * | 2021-09-30 | 2023-04-06 | 中国石油化工股份有限公司 | ETHYLENE-α-OLEFIN COPOLYMER, PREPARATION METHOD THEREFOR, APPLICATION AND COMPOSITION THEREOF |
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| US7910669B2 (en) * | 2009-03-17 | 2011-03-22 | Chevron Phillips Chemical Company Lp | Methods of preparing a polymerization catalyst |
| CN112142956B (en) * | 2020-09-27 | 2021-10-19 | 中国科学院物理研究所 | Polymerization method of carbon monoxide |
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| CO6571848A2 (en) | 2012-11-30 |
| SG174405A1 (en) | 2011-10-28 |
| US20100240844A1 (en) | 2010-09-23 |
| US8697599B2 (en) | 2014-04-15 |
| MX2011009795A (en) | 2011-10-17 |
| EP2408826B1 (en) | 2015-07-15 |
| CN102356098B (en) | 2014-11-05 |
| BRPI1009883A2 (en) | 2016-03-08 |
| WO2010107478A1 (en) | 2010-09-23 |
| US20110136996A1 (en) | 2011-06-09 |
| KR101667830B1 (en) | 2016-10-19 |
| US7910669B2 (en) | 2011-03-22 |
| ES2543609T3 (en) | 2015-08-20 |
| EP2408826A1 (en) | 2012-01-25 |
| KR20110129393A (en) | 2011-12-01 |
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